The structural, dielectric, dynamical, elastic, piezoelectric and nonlinear optical (second-order susceptibility and Pockels tensors) properties of Bi2WO6 in its P21ab ferroelectric ground state are determined using density functional theory. The calculation of infrared and Raman spectra on single crystal allowed us to clarify the assignment of experimental phonon modes, considering the good agreement between the calculated and the experimental Raman spectra obtained on polycrystal. The calculation of the elastic constants con rms the elastic stability of the crystal and allow us to estimate the Young and shear moduli of polycrystalline samples. The piezoelectric constants have signi cant intrinsic values comparable to those of prototypical ABO3 ferroelectrics. The electro-optic response is strongly dominated by the ionic contribution of transverse optic modes, yielding sizable Pockels coe cients around 9 pm/V along the polar direction. [less ▲]

In order to better understand the reconstructive ferroelectric-paraelectric transition of Bi2WO6, which is unusual within the Aurivillius family of compounds, we performed first-principles calculations of ... [more ▼]

In order to better understand the reconstructive ferroelectric-paraelectric transition of Bi2WO6, which is unusual within the Aurivillius family of compounds, we performed first-principles calculations of the dielectric and dynamical properties of two possible high-temperature paraelectric structures—the monoclinic phase of A2/m symmetry observed experimentally and the tetragonal phase of I4/mmm symmetry—common to most Aurivillius-phase components. Both paraelectric structures exhibit various unstable modes, which, after their condensation, bring the system toward more stable structures of lower symmetry. The calculations confirm that, starting from the paraelectric A2/m phase at high temperatures, the system must undergo a reconstructive transition to reach the P21ab ferroelectric ground state. [less ▲]